Chemistry Department, Brock University, 500 Glenridge Avenue, St. Catharines, Ontario L2S 3A1, Canada.
J Am Chem Soc. 2011 May 4;133(17):6487-9. doi: 10.1021/ja111748u. Epub 2011 Apr 8.
A 1:1:1 reaction between complex (Tp)(ArN═)Mo(H)(PMe(3)) (3), silane PhSiD(3), and carbonyl substrate established that hydrosilylation catalyzed by 3 is not accompanied by deuterium incorporation into the hydride position of the catalyst, thus ruling out the conventional hydride mechanism based on carbonyl insertion into the M-H bond. An analogous result was observed for the catalysis by (O═)(PhMe(2)SiO)Re(PPh(3))(2)(I)(H) and (Ph(3)PCuH)(6).
复合物(Tp)(ArN═)Mo(H)(PMe(3))（3）、硅烷 PhSiD(3)和羰基底物之间的 1:1:1 反应表明，3 催化的氢硅烷化反应不会导致催化剂中氢化物位置的氘掺入，从而排除了基于羰基插入 M-H 键的传统氢化物机理。类似的结果也观察到了(O═)(PhMe(2)SiO)Re(PPh(3))(2)(I)(H)和(Ph(3)PCuH)(6)的催化作用。
